Lubricants



aoow oom. ono oon A. A. MANTEUFFEL ET AL LUBRICANTS Filed Dec. 18, 1956 Aug. 18, 1959 0 o 'D Q (961m sAulaav uvsloasmfl INVENTORS ALLAN A. MANTEUFFEL vGEORGE R. cook BY WARREN w. coRTlss A'rToRN-EY (United States Patent Plaines, and Warren W. Cortiss, Crystal Lake,rIll.,A assignors to The Pure Oil Company, Chicago, Ill.,fa-cor poration of Ohio .A

Application December 18, 1956, Serial No.'62197,0 7'6 ks claims. ((1252-57) This invention relates to the use of epoxidized alkyl esters of unsaturated fatty acids as lubricants, both with and without a mineral oil base, and to a process of lubricating, using the aforementioned compounds per se and with a'lubricating oil.

Fatty epoxides are used as polyvinyl chloride plasticizers and stabilizers for various plastics. Also, the development of uses of fatty epoxides has gone forward Ybecause of the improved methods of preparation which acids which are potential plasticizers Aor Vconstituents of lubricating compositions used in jet engines. Lead tetraacetate may be the cleavage agent, as may periodic acid, potassium permanganate, sodium bismuthate, certainorganic 'iodoso diacetates, chromic acid, and chromyl chloride. Another reaction of fatty epoxides is that with ammonia or amines to form alkylolamines As is commonly known at this time, epoxy derivatives may react with or replace polyhydric alcohols and polycarboxylic acids or their anhydrides to form alkyl-type resins or epoxy resins. Soybean oil which has been epoxidized with hydrogen peroxide has been used in resiny adhesive formulations to impart better vtensile strength. There are other indications inthe art that epoxidized fatty materials are useful in the preparation of modified products. Thus, by subjecting fatty epoxides to pyrolysis,-'conju gated dienes are formed, useful as drying oils which dry rapidly, giving tacky films because of the predominance pounds such as mercaptans to form flotation agents,

and hydrogenation and reduction.

mineral lubricating oils.

ice

For these purposes, compounds Vof, the' formula:

R-HamcH-cH-wHm-c Vwhere R is selected from'the group of alkyl radicalsof Y Y1 to.6 carbon atoms-R -is selected from the groupj'of fas alkylmadicals of l'to 8 carbon atoms, m is an integer `of from 0 to 7, and 'n is an integer of from 5 to 7, mmay Vbensed. The 'unsaturated fatty acids may be selected from the acids present in fats and oils,'such^as"lauro1'eic .(C12H22O2), myristoleic (CMHZGO'g), palmitoleic i C16H30O2) oleic (cm1-1:3402) gadoleic (CZOHggOz) eruCiC (C22H42O2) ri'c'inoleic V(C18H3403), linoleic (ClgHgzOz), linolenic (ClgHgoOz), eleostearic (C18H30O2), licanic C18H25O3'), arachidom'c (Cmd-13202) and clupanodonic (C22H36O2). These various fatty acids may be epoxidized and then esteriied, or the esteritication may precede 'the epoXidation. VSince epoxidation results in the saturation` of the carbon chain of the acid, the chemical name for the end product changes to that of its saturatedform. Thius, epo'ir'idized methyl oleate would becomeY methyl 'epoxy stearate. p l

It becomes then a primary objectvof this invention to provide a lubricant comprising compounds of the formula: v

R-(cnnm-cnoH-(onao/ where R is an alkyl group having l to 6 carbon atoms, R is an alkyl radical having from l to 8 carbon atoms, m is an integer of from 0 to 7 and n is an integer Vof from 5 to 7.

A second object of the invention is to provide a lminrcontact, therewith a composition comprising epoxidized The present invention is based on the discovery-/that epoxidized fatty materials have lubricating properties'iid Ya arent as the d'escri tio th f of trans double linkages 1n the pyrolysls product. Other- Y pp p n ereo proceeds reactions include the'addition of active hydrogen"coin-f1.'vvv

above general formula. y, rlll'esev and otherfobjects of theinvention will alkyl esters of unsaturated fatty acids coming within the 'In order to demonstrate the invention, a series of experiments WereAconducted on a number of mineral oil ,compositions containing various Lamounts of lard oil,

' lmineral 'oil compositions containing various amounts of `epoxidifzed fattyesters coming within the scope lof the invention, and mineral oil without the presence of a load- 6Ncarrying agent. The results are shown in the following A table vincluding stability tests and Farlex tests.

become Table I Com i i nh wt. ereent Stab. 90 da s pos t o y p y Falex Max TLoad Blend Fat oil orque 80 Vis. 200 Vis. ty 120 F. Approx. Test Neat. Neut. 80 F. (pounds) Amount Type 68 28 4 Lard nil Pass- Pass 806 88 7 do dn Borderline-- 813 5 84 11 do in Sepn- 840 5 77 18 do rio 920 5 72 23 ---do do dn 940 50 50 do o (in l, 193 100 dn rln fin 2,050 71 29 flo Pass 666 95 'in fin 641 70 29 1 Epoxidized methyloleate-- --dO do 764 Y 70 28 2 dn rio flo 822 68 28 4 fin dn rln 1,008 i 5 72 23 dn ri fin 1,476

50 50 rin Il fin 1, 956V rin in dn 1,875 68 28 4 Methyl esters of animal Cloudy---" Cloudy----- 850 fatty acids. 5 72 23 dn Sediment--- Sediment--- 925 68 28 4 Butyl esters of animal ass Pass 772 Y fatty acids.

5 72 23 dn rln dn 925 6 71 23 Epoxdized soybean oil do do 1, 155

ae 6 71 23 Iso-octyl epoxy stearato- 'in do 1, 082 6 7l 23 Butyl epoxy stearato do Y l o 1, 086 6 71 23 Epogrdized soybean oil ---.-d0.--.-.- ---..do 1, 580

aci 6 71 23 Methyl epoxy stearatofin an 1, 082

Referring to Table I, the value under Falex max. load torque test represents an average of 8 to 10 runs using a Falex #l0 journal. Blends 1-5 represent lubricating compositions containing mineral oil as the major component with lard oil as the minor component representing the fatty oil constituent. Such compositions are commercially available and are primarily used where a moderate level of lubrication is required as in cutting oil compositions. Blends 6 and 7 further illustrate the fatty oil type of composition, with the fatty oil being a major component in Blend 6 and the only component in Blend 7. Blends 10 through 14 are exemplary of compositions made in accordance with this invention, each containing epoXidized methyl oleate (EMO) and mineral oil. Even though Blend 15, consisting of epoxidized methyl oleate alone, is not equal to lard oil alone (Blends 1-5) in lubricity, as measured lby the Falex maximum-load torque test, a comparison of Blends 10-14 with Blends 1-6 shows that the combination of EMO and mineral oil is superior 4to lard oil and mineral oil. Comparison of Blends 10-15 with 16 and 17 shows the eiect of epoxidiaztion Blends 16J-19 show the relative ineiectveness of varying amounts of methyl and butyl esters of animal fatty acids. Blends 20-24 are further illustrative of the invention using epoxidized fatty materials. The epoXidized soybean oil acid of blend 20 diiered slightly in physical properties from that of Blend 23 as will be shown subsequently. Ihe methyl epoxy stearate used in Blend 24 is a diierent source material than that used in Blends 10-15; both being epoxidized methyl oleate, but having different physical properties.

J The Vsuperiority of epoxidized fatty material-mineral Oilblends over lard oil-mineral oil blends is shown by reference to the diagram of this invention wherein the curves show that EMO-containing blends are superior to Ylard oil'blends, even up to a concentration greater than 50% by weight. The broken portions of the curves representextrapolations of the experimental data andv indicate that the compositionsl of this invention are superior up to an EMO concentration of or more. For economic reasons, the upper concentration of epoxidized fatty-material is preferably limited to about 50% by weight. t Y

, The mineral oils used in these experiments 'had the following characteristics:

Table Il 85-100 High VI N eut. 200-85 Intermediate VI N eut.

Flash, F 395 Flash, F 455 Fire, F 440 Fire, F 490 Vis. F., SUS-- 82. 1 Vis. 100 F., SUS.--.- 213.3 Vis. 210 F., SU 37.8 Vis. 210 F., SUS----- 46.8 Vis.V Index 100 Vis. Index 91 .Color (ASTM). 1+ Color (ASTM). +2 Pour Point, F 0 our Point, 0 Car. Residue, p 0.01 Car. Residue, pe 0. 04 Sulfur, percent.-- 0. 07 Sulfur, percent- 0. 44 Acid N0. (l948).---- 0. 03 Acid No. (1948)- 0.07

The physical properties of the epoxidized fattyV materials used in the foregoing experiment are shown in Table III.

Table III Butyl Epoxidized Epoxidized Iso-octyl Epoxidized Epoxy Soybean Soybean epoxy Epoxy-Fatty Material meth Stearate oil acid oil acid stearato 4oleate (#10-15) (#22) (#23) (#20 Physical Characteristics: L

Y Oxirane,` percent 6-6A 6.4 3.0-8.0 Iodine N o 4.0-6.0 l 0-3.0 2. 0-4.0 0.3 0.3 1.0 r 18o l night) alghe aight) Mild The esters of animal fatty acids, before epoxidization, hadv the following characteristics:

Numerous examples of epoxidized alkyl esters of unsaturated fatty acids coming within the general formula heretofore discussed `are expressed as follows. The number appearing beforethe epoxy as 7-epoxy indicates the location of the epoxy linkage between the 7th and 8th carbon atoms of the fatty acid chain. Thus 9-epoxy isopropyl tridecoate has the epoxy linkage at the 9th and 10th carbon atoms.

9-epoxy propyl laurate 9epoxy isopropyl laurate 9-epoxy butyl laurate 9-epoxy sec-butyl laurate 9-epoxy iso-butyl laurate 9-epoxy tert-butyl laurate 7-epoxy methyl caprate 7-epoxy methyl undecoate 7-epoxy ethyl undecoate 7epoxy propyl undecoate 7-epoxy isopropyl undecoa'te 7-epoxy butyl undecoate 7-epoxy isobutyl undecoate 7-epoxy ethyl caprate 7-epoxy sec-butyl 7-epoxy propyl caprate undecoate 7-epoxy isopropyl caprate 7-epoxy tert-butyl 7-epoxy butyl caprate undecoate 7-epoxy` sec-butyl caprate S-epoxy methyl laurate 8-epoxy ethyl laurate S-epoxy propyl laurate 8-epoxy isopropyl laurate S-epoxy butyl laurate 8-epoxy isobutyl laurate 8-epoxy sec-butyl laurate S-epoxy tert-butyl laurate 9-epoxy methyl tridecoate 7-epoxy iso-butyl caprate 7-epoxy tert-butyl caprate S-epoxy methyl undecoate S-epoxy ethyl undecoate 8-epoxy propyl undecoate 8-epoxy isopropyl undecoate 8-epoxy butyl undecoate 8-epoxy sec-butyl 9-epoxy ethyl tridecoate undecoate 9-epoxy propyl tridecoate S-epoxy iso-butyl 9-epoxy isopropyl undecoatetridecoate S-epoxy tert-butyl 9-epoxy butyl tridecoate undecoate 9epoxy isobutyl tridecoate 9epoxy sec-butyl 9-epoxy methyl myristate 9-epoxy ethyl myristate tridecoate 9-epoxy propyl myristate 9-epoxy tert-butyl 9-epoxy isopropyl tridecoate myristate 7-epoxy methyl tridecoate 7-epoxy ethyl trideccate 9-epoxy butyl myristate 9-epoxy sec-butyl 7-epoxy propyl tridecoate myristate 7-epoxy isopropyl 9-epoxy iso-butyl tridecoate myristate 7-epoxy butyl tridecoate 9-epoxy tert-butyl 7-epoxy isobutyl tridecoate myristate 7-epoxy sec-butyl 9-epoxy methyl pentatridecoate decoate 7-epoxy tert-butyl 9-epoxy ethyl pentatridecoate decoate 7-epoxy methyl laurate 9-epoxy propyl penta- 7-epoxy ethyl laurate decoate 6A Y f t l Seiner. isopropyl renta-` ldecoate 9-epoxy butyl pentadecoate `9-epoxy sec-butyl penta- 7-epoxy propyl laurate 7-epoxy isopropyl laurate 7-epoxy butyl laurate 7-epoxy isobutyl laurate 7epoxy sec-butyl laura'te decoate 7-epoxy tert-butyl 9-epoxy iso-butyl pentatridecoate decoate i v 8-epoxy methyl tridecoate 9-epoxy tert-butyl penta- S-epoxy ethyl tridecoate decoate t 8-epoxy propyl tridecoate 8-epoxy isopropyl tridecoate 8,-epoxy butyl tridecoate 8-epoxy isobutyl trideco-ate 8-epoxy sec-butyl 9-epoxy methyl tricosoate 9.epoxy ethyl behenate '9-epoxy propyfl arachidate 9t-epoxy isopropyl non decoate 9-epoxy butyl stearafte` i tridecoate '9fepoxy methyl` stearateV S-epoxy tert-butyl 9-epoxy ethyl stearate tridecoate 9-epoxy propyl stearate 7 -epoxy methyl pelargonate 7-epoxy ethyl pelargonate 7-epoxy propyl pelargonate 7-epoxy isopropyl pelarognate 7-epoxy butyl pelargonate 9-epoxy isopropyl stearate 9-epoxy iso-butyl stearate 9-epoxy sec-butyl stearate 9-epoxy tert-butyl stearate 8-epoxy methyl heneicosoate 8-epoxy ethyl nondecoate pelargonate 7-epoxy propyl margaroate 7-epoxy iso-butyl 7epoxy isopropyl pelargonate palmititate 7epoxy tert-butyl S-epoxy methyl myristate pelargonate S-epoxy ethyl myristate S-epoxy methyl caprate S-epoxy ethyl caprate 8-cpoxy propyl caprate 8-epoxy isopropyl caprate 8-cpoxy butyl caprate S-epoxy propyl myristate 8-epoxy isopropyl myristate 8-epoxy butyl myristate 8-epoxy sec-butyl S-epoxy sec-butyl caprate myristate 8-epoxy iso-butyl caprate S-epoxy iso-butyl S-epoxy tert-butyl caprate myristate 9-epoxy methyl undecoate S-epoxy tert-butyl 9-epoxy ethyl undecoate myristate 9-epoxy propyl undecoate 9-epoxy isopropyl undecoate 9-epoxy butyl undecoate 9-epoxy sec-butyl 7-epoxy methyl myristate 7epoxy ethyl myristate 7-epoxy propyl myristate 7-epoxy isopropyl myristate The position of the epoxy group is seen to vary from attachment between the 9-10 carbon atoms, the 8-9 carbon atoms and 7-8 carbon atoms. The afore-designated epoxy positions have been called 9-epoxy-, 8epoxy and 7-epoxy compounds, respectively, for purposes of this description. The invention is not to be limited to these compounds and the epoxy group may be situated at other positions in the carbon atom chain. In general, straight-chain alkyl groups are included in the delni-tion of R with l to 6 carbon atoms, forming fthus the aliphatic monobasic acid series. The alkyl groups included in the definition of R are methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, iso-butyl tertiary butyl groups, up to and including octyl. Either naturally-occurring or synthetic esters may be used in preparing the epoxidized fatty materials found useful in this invention. useful application of `the epoxidized fatty materials of this ,invention is in cutting oil compositions.

What is claimed is:

1. A lubricating oil composition, exhibiting loadcarrying ability, comprising a mineral lubricating oil and from about 1.0 to about 50.0 weight percent of an One particularly v epoxidized alkyl ester of an unsaturated fatty acid, said esters having the general formula i I OR,

whereinzR is an alkyl radical of 1 to 6 carbonatom's, m is an integer 'of from 0 to 7, n is an integer of from 5 to 7, and R is an alkyl group of 1 to 8 'carbon atoms.

claim l in which R is a straight-chain saturated alkyl group of from l to 6 carbon atoms.

3. A lubricantin accordance with claim 1 in which said ester is 9-epoxy methyl stearate.

4. A lubricant in accordance with claim 1 in which said ester is butyl epoxy stearate.

8 5. A lubricant inV accordance with claim l in which said ester is an epoxidizedester obtained from soybean oil acids having an oxirane content of about 6.4% and an iodine value of from 4.0 to 6.0.

6. A lubricating oil in accordance with claim 1 in which said ester is an epoxdized C1-C8 alkyl oleate.

7. A lubricant gin accordance with claim l in which said ester is an epoxidized Cl-Cg alkyl stearate.

8. A lubricant in accordance with claim 1 in which 2. A lubricating oil composition inf accordance -With 10 S-ald esteris epoxldlzed methyl oleate' References Cited in the le of this patent UNrrED STATES PATENTS Colbeth Aug.. 6, 1940 McDermott Feb. 20, 1951 Findley et al. Sept. 18, 1951 

1. A LUBRICATING OIL COMPOSITION, EXHIBITING LOADCARRYING ABILITY, COMPRISING A MINERAL LUBRICATING OIL AND FROM ABOUT 1.0 TO ABOUT 50.0 WEIGHT PERCENT OF AN EPOXIDIZED ALKYL ESTER OF AN UNSATURATED FATTY ACID, SAID ESTERS HAVING THE GENERAL FORMULS 